JP2003238609A - Method for producing polymer from radical- polymerizable monomer - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a method for producing a polymer obtained from a radical- polymerizable monomer utilizing an atomic transfer-type radical polymerization method in which handling of a catalyst is facilitated and the initiator system can allow a wide selection range of initiators. <P>SOLUTION: This method employs as the initiator an organic halogenated compound or a halogenated sulfonyl compound, carries out polymerization of at least one kind of a radical-polymerizable monomer in the presence of a redox catalyst comprising a metal complex expressed by formula (1): (M)<SP>n+1</SP>Z<SB>m</SB>(wherein M represents at least one kind of transition metal selected from 7 to 11 groups of the periodic table; n is an integer of 1 or more; m is an integer of 1 to 4; (M)<SP>n+1</SP>represents a high atomic value state which can be reduced; Z represents organic ligands coordinating via oxygen atoms, nitrogen atoms, phosphorus atoms, sulfur atoms or carbon atoms). <P>COPYRIGHT: (C)2003,JPO

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for producing a polymer containing a radical-polymerizable monomer, and more particularly to a production method utilizing an atom transfer type radical polymerization method.

[0002]

2. Description of the Related Art Various polymerization methods for controlling structures such as molecular weight, molecular weight distribution, monomer species and functional group distribution have been studied for the production of functional polymers. One of them is
The following two initiation systems are known in the atom transfer radical polymerization method that has been studied conventionally. In both (1) and (2) below, the high-valence metal and the low-valence metal have a one-electron redox relationship.

(1) Initiating system using a low-valent metal complex having a halogen atom and an organic halogenated compound. (2) Initiating system using a high valent metal complex having a halogen atom and a radical initiator.

However, in any of the above-mentioned initiation systems, only a catalyst of a metal complex having a halogen atom is known, and there is a problem that the selection range of the metal complex used as the catalyst is narrow.

Further, in the case of the initiation system of the above (1), the low valence complex compound used as a catalyst is expensive and relatively unstable and is easily oxidized to a high valence state, which makes the handling of the catalyst complicated. On the other hand, in the case of the above-mentioned (2) initiation system, it is difficult to use a bifunctional or higher-functional initiator as an initiator, and in order to obtain three or more block polymers, the polymerization process has three or more steps. However, any of the starting systems is industrially problematic in terms of operability and cost.

[0006]

SUMMARY OF THE INVENTION The present invention has been made in view of the above circumstances, and an object thereof is a method for producing a polymer comprising a radical-polymerizable monomer, in which the catalyst can be easily handled and started. An object of the present invention is to provide a production method by an atom transfer type radical polymerization method using an initiation system having a wide selection range of agents.

[0007]

As a result of intensive studies, the present inventors have found a catalyst for a redox composed of a metal complex having no halogen atom, and completed the present invention.

That is, the gist of the present invention is to use an organic halide or a sulfonyl halide compound as a polymerization initiator in the presence of at least one redox catalyst consisting of a metal complex represented by the following general formula (1). A method for producing a polymer comprising a radical-polymerizable monomer, which comprises polymerizing at least one radical-polymerizable monomer.

[0009]

Embedded image (M) ^{n + 1} Z _m (1) (where M is at least one transition metal selected from Groups 7 to 11 of the periodic table, n is an integer of 1 or more, m is an integer of 1 to 4, (M) ^{n + 1} is a high valence state that can be reduced, and Z is
It represents an organic ligand coordinated with an oxygen atom, a nitrogen atom, a phosphorus atom, a sulfur atom or a carbon atom. )

[0010]

BEST MODE FOR CARRYING OUT THE INVENTION The present invention will be described in detail below.
The present invention is a method for producing a polymer using an atom transfer radical polymerization method. The atom transfer radical polymerization method is represented by the following scheme.

[0011]

[Chemical 3]

In the above, P is a polymer or an initiator,
(M) is a transition metal, X is a halogen or pseudohalogen, Y
And L are ligands capable of coordinating to (M), n and n + 1
Is the valence of the transition metal, and the low valence complex (1) and the high valence complex (2) form a redox conjugated system.

First, the low valence complex (1) radically abstracts the halogen atom X from the organic halide PX to form the high valence complex (2) and the carbon-centered radical P. Is represented by Kact). This radical P · reacts with the monomer to form an intermediate radical species P · of the same kind as shown in the figure (the rate of this reaction is K
Represented by ProPagation). The reaction between the high valence complex (2) and the radical P · produces the product PX and at the same time regenerates the low valence complex (1) (the rate of this reaction is represented by Kdeact). . And low valence complex (1)
Further reacts with PX to advance a new reaction. In this reaction, suppressing the concentration of the growing radical species P to be low is the most important in controlling the polymerization.

In the present invention, the polymerization solvent is water,
Ether compounds such as diethyl ether, tetrahydrofuran, diphenyl ether, anisole, dimethoxybenzene, nitrile compounds such as acetonitrile, propionitrile, benzonitrile, N, N-dimethylformamide, N, N-dimethylacetamide, acetone, methyl ethyl ketone, methyl isobutyl ketone Carbonyl compounds such as ethyl acetate, butyl acetate, ethylene carbonate, propylene carbonate, methanol, ethanol,
Alcohol compounds such as propanol, isopropanol, n-butyl alcohol, t-butyl alcohol, isoamyl alcohol, etc., aliphatic and aromatic hydrocarbon compounds such as benzene, toluene, hexane, heptane, octane, halogens such as methylene chloride, chloroform and chlorobenzene. Compound. In the present invention, the use of the polymerization solvent is optional.

The amount of the polymerization solvent used is not particularly limited, but is usually 1 to 2 with respect to 100 parts by weight of the charged monomer.
000 parts by weight, preferably 10 to 1000 parts by weight.

In the present invention, the organic halide or the sulfonyl halide compound used as the polymerization initiator is a compound having at least one halogen serving as a polymerization initiation point (also referred to as a polymerization initiation terminal or a initiation terminal). There is no particular limitation as long as it is present, but it is usually a compound having one or two halogens as starting points, and compounds represented by the following general formulas (1) to (19) are preferable. However, in the general formulas (1) to (19), C ₆ H ₅ is a phenyl group, C ₆ H ₄ is a phenylene group, and R ¹ and R ² are
A hydrogen atom, an alkyl group having 1 to 20 carbon atoms, an aryl group or an aralkyl group, which may have a functional group such as an alcoholic hydroxyl group, an amino group, a carboxyl group or an alkylthio group on each carbon atom, Also, they may be the same or different. X is chlorine, bromine or iodine, and n is an integer of 0-20.

<Polymerization Initiator with One Starting Point> (1) C ₆ H ₅ -CH ₂ X (2) C ₆ H ₅ C (H) (X) CH ₃ (3) C ₆ H ₅ -C ( _{X) (CH 3) 2 (} 4) R 1 -C (H) (X) -CO 2 R 2 (5) R 1 -C (CH 3) (X) -CO 2 R 2 (6) R 1 - C (H) (X) -C (O) R 2 (7) R 1 -C (CH 3) (X) -C (O) R 2 (8) R 1 -C 6 H 4 -SO 2 X

<Polymerization Initiator with Two Starting Points> (9) o-, m-, p-XCH ₂ -C ₆ H ₄ -CH ₂ X (10) o-, m-, p-CH ₃ C ( _{H) (X) -C 6 H} 4
-C (H) (X) CH 3 (11) o-, m-, p- (CH 3) 2 C (X) -C 6 H 4 -
_{C (X) (CH 3)} 2 (12) RO 2 C-C (H) (X) - (CH 2) n -C
_{(H) (X) -CO 2} R (13) RO 2 C-C (CH 3) (X) - (CH 2) n -C
_{(CH 3) (X) -CO} 2 R (14) RC (O) -C (H) (X) - (CH 2) n -C
(H) (X) -C ( O) R (15) RC (O) -C (CH 3) (X) - (CH 2) n -
_{C (CH 3) (X)} -C (O) R (16) XCH 2 CO 2 - (CH 2) n -OCOCH 2 X (17) CH 3 C (H) (X) CO 2 - (CH 2) _n- OCO
C (H) (X) CH 3 (18) (CH 3) 2 C (X) CO 2 - (CH 2) n -OCO
C (X) (CH ₃ ) ₂ (19) RC (O) CH (X) ₂

Examples of the polymerization initiator represented by the general formula (1) include phenylmethyl chloride, phenylmethyl bromide, phenylmethyl iodide, and the like. Examples of the polymerization initiator represented by the general formula (2) include 1-phenyl. As the polymerization initiator represented by the general formula (3), such as ethyl chloride, 1-phenylethyl bromide, 1-phenylethyl iodide, 1-phenylisopropyl chloride, 1-phenylisopropyl chloride
Examples of the polymerization initiator represented by the general formula (4) such as phenylisopropyl bromide and 1-phenylisopropyl iodide include 2-chloropropionic acid, 2-bromopropionic acid, 2-iodopropionic acid, and 2-chlorobutanoic acid. 2-Bromobutanoic acid, 2-iodobutanoic acid, methyl-2-chloropropionate, ethyl-2-chloropropionate, methyl-2-bromopropionate, ethyl-2-bromopropionate, methyl-2- As the polymerization initiator represented by the general formula (5) such as iodopropionate, 2-chloroisobutanoic acid, 2-bromoisobutanoic acid, 2-iodoisobutanoic acid, methyl-2-chloroisobutyrate, ethyl- 2-chloroisobutyrate, methyl-2-bromoisobutyrate, ethyl-2-bromoisobutyrate, Chill-2-iodo isobutyrate,
As the initiator represented by the general formula (6), such as ethyl-2-iodoisobutyrate, α-chloroacetophenone,
α-bromoacetophenone, α-chloroacetone, α-
Examples of the initiator represented by the general formula (7) such as bromoacetone include α-chloroisopropyl phenyl ketone and α-bromoisopropyl phenyl ketone, and examples of the initiator represented by the general formula (8) include p-toluene. Examples of the initiator represented by the general formula (9), such as sulfonyl chloride and p-toluenesulfonyl bromide, include α, α′-dichloroxylene, α, α′-dibromoxylene, α, α′-diiodoxylene, and the like. Examples of the initiator represented by the general formula (10) include bis (1-chloroethyl) benzene and bis (1
Examples of the initiator represented by the general formula (11) such as -bromoethyl) benzene include bis (1-chloro-1-methylethyl) benzene and bis (1-bromo-1-ethyl) benzene. ), The initiator is 2,
Dimethyl 5-dichloroadipate, Dimethyl 2,5-dibromoadipate, Dimethyl 2,5-diiodoadipate, Diethyl 2,5-dichloroadipate, Diethyl 2,5-dibromoadipate, 2,5-Diiodo Diethyl adipate, dimethyl 2,6-dichloro-1,7-heptanedioate, dimethyl 2,6-dibromo-1,7-heptanedioate, dimethyl 2,6-diiodo-1,7-heptanedioate, 2 , 6-dichloro-1,7-heptanedioate diethyl, 2,6-dibromo-1,7-heptanedioate diethyl, 2,6-diiodo-1,7-heptanedioate diethyl, etc., the general formula (13) The initiator represented by
-Dichloro-2,6-dimethyl-1,7-heptanedioate dimethyl, 2,6-dibromo-2,6-dimethyl-1,
Examples of the initiator represented by the general formula (14) such as dimethyl 7-heptanoate include 3,5-dichloro-2,6-heptanedione, 3,5-dibromo-2,6-heptanedione and the like. As the initiator represented by (15), 3,5
-Dichloro-3,5-dimethyl-2,6-heptanedione, 3,5-dibromo-3,5-dimethyl-2,6-heptanedione and the like, as the initiator represented by the general formula (16), As the initiator represented by the general formula (17) such as ethylene glycol bis (2-bromoacetic acid) ester, ethylene glycol bis (2-bromopropionic acid) ester, ethylene glycol bis (2-chloropropionic acid) ester, Examples of the initiator represented by the general formula (18) include ethylene glycol bis (2-bromoisobutyric acid) ester and ethylene glycol bis (2-chloroisobutyric acid) ester. , Α, α-dichloroacetophenone, α, α-dibromoacetophenone and the like.

In the present invention, a redox catalyst composed of a metal complex represented by the following general formula (1) is used.

[0021]

Embedded image (M) ^{n + 1} Z _m (1) (where M is at least one transition metal selected from Groups 7 to 11 of the periodic table, n is an integer of 1 or more, m is an integer of 1 to 4, (M) ^{n + 1} is a high valence state that can be reduced, and Z is
It represents an organic ligand coordinated with an oxygen atom, a nitrogen atom, a phosphorus atom, a sulfur atom or a carbon atom. )

The above high valence metal (M)^{n + 1}as,
Cu²⁺, Ni⁺, Ni²⁺, Ni³⁺, Pd⁺, Pd²⁺, Pt
⁺, Pt²⁺, Pt³⁺, Rh²⁺, Rh³⁺, Rh⁴⁺, C
o²⁺, Co ³⁺, Ir⁺, Ir²⁺, Ir³⁺, Ir⁴⁺, Fe
³⁺, Ru³⁺, Ru⁴⁺, Ru⁵⁺, Ru^{Five +}, Os³⁺, O
s⁴⁺, Re³⁺, Re⁴⁺, Re⁵⁺, Re⁷⁺, Mn³⁺, Mn
⁴⁺At least one selected from the group this
Among them, Cu²⁺, Ni⁺, Ni²⁺, Ni³⁺, Pd⁺,
Pd²⁺, Co²⁺, Co³⁺, Fe³⁺, Ru³⁺, Ru⁴⁺, R
u⁵⁺, Ru⁵⁺, Re³⁺, Re⁴⁺, Re⁵⁺, Re⁷⁺A group of
One selected from the group is preferably Cu²⁺, Ni³⁺, Fe³⁺,
Ru³⁺, Ru⁴⁺More preferably one selected from the group of C
u²⁺Or Fe³⁺Is particularly preferable, and Cu²⁺Is most preferred
Yes.

The metal-coordinating atom of the organic ligand Z is preferably an oxygen atom or a nitrogen atom.
The organic ligand Z is a monodentate to tetradentate ligand, preferably a monodentate to bidentate ligand.

Specific examples of the organic ligand Z include the following. That is, as the monodentate ligand, acetoxy group, trifluoroacetoxy group, toluenesulfonyloxy group, trifluoromethanesulfonyloxy group, triphenylphosphino group, tributylphosphino group, sulfuric acid group, phosphoric acid group, pyrophosphoric acid group , Hydroxyl group, 1 to 1 carbon atoms
Examples thereof include an alkoxy group containing an aliphatic or aromatic alkyl group of 0, the same alkylthio group, and the like. Examples of the bidentate ligand include an acetylacetonato group and 2,2,6,6-tetratrifluoroacetylaceto group. Examples of the tridentate ligand include diethylenetriamine and the like, and examples of the tetradentate ligand include a porphyrin group and a phthalocyanine group.

Among the metal complexes of the general formula (1), Cu ²⁺ Z _m
As specific examples of, cupric acetate, bis (trifluoromethanesulfonic acid) copper (II), bis (acetylacetonato) copper (II), 2,2,6,6-tetramethyl 3,5-
Heptane dionato copper (II), hexafluoroacetylacetonato copper (II), copper (II) hydroxide, dimethoxy copper (I
I), porphyrin copper (II) and its derivatives, phthalocyanine copper (II) and its derivatives, copper pyrophosphate (II),
Examples thereof include copper (II) sulfate and copper (II) trifluoroacetate. Especially bis (trifluoromethanesulfonic acid) copper (I
I) is preferred.

In the metal complex ((M) ^{n + 1} Z _m ), an organic ligand Z may be used together with another organic ligand L.
Such an organic ligand L is used to further promote solubilization in a polymerization solvent and reversible conversion of a redox conjugated complex. As the coordination atom to the metal of the organic ligand L,
An oxygen atom, a nitrogen atom, a phosphorus atom or a sulfur atom can be mentioned, but an oxygen atom, a nitrogen atom or a phosphorus atom is preferable. Further, the organic ligand L may have two or more kinds of coordination atoms, and in particular, has three or more coordination atoms and 2 or more coordination atoms.
It is preferably at least one species. When the metal complex is a copper complex, the organic ligand L is preferably a nitrogen atom alone or an organic ligand having nitrogen and oxygen atoms.

The metal complex and the compound which forms the organic ligand L may be added separately to form the metal complex in the polymerization system. Alternatively, the organic ligand Z and the organic ligand L may be prepared in advance. You may synthesize | combine the metal complex which has and add it to a polymerization system.
In particular, in the case of copper, the former method is preferable, and ruthenium,
In the case of iron and nickel, the latter method is preferable.

Specific examples of the compound which produces the organic ligand L include 2,2'-bipyridyl and its derivatives, 1,10-phenanthroline and its derivatives, and tetramethylethylenediamine when the number of coordination atoms is one. , Pentamethyldiethylenetriamine, hexamethyltris (2-
Aminoethyl) amine, triphenylphosphine, tributylphosphine and the like, and when there are two or more coordination atoms, triethanolamine, 2-pyridinol,
6 '-{2-exo-hydroxy-1,7,7-trimethylbicyclo [2.2.1] heptan-2-end-yl}
2,2'-bipyridine etc. are mentioned.

Among the metal complexes having the organic ligand Z and the organic ligand L synthesized in advance, specific examples of the ruthenium, iron and nickel complexes include tris (2,2,6,6-tetramethyl- 3,5-heptanedionato) ruthenium (III), triacetylacetonato iron (III), bis (acetylacetonato) nickel (II) and the like can be mentioned.

The radical-polymerizable monomer used in the present invention can be used without limitation as long as it is an ordinary radical-polymerizable monomer. As such a monomer, an acrylate monomer, a methacrylate monomer or a styrene derivative is preferably used.

Specific examples of the above-mentioned monomer include methyl (meth) acrylate, ethyl (meth) acrylate,
Propyl (meth) acrylate, n-butyl (meth) acrylate, t-butyl (meth) acrylate, hexyl (meth) acrylate, 2-ethylhexyl (meth)
Acrylate, nonyl (meth) acrylate, benzyl (meth) acrylate, cyclohexyl (meth) acrylate, lauryl (meth) acrylate, n-octyl (meth) acrylate, 2-methoxyethyl (meth) acrylate, butoxyethyl (meth) acrylate, Methoxytetraethylene glycol (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-
Hydroxypropyl (meth) acrylate, 3-chloro-2-hydroxypropyl (meth) acrylate, tetrahydrofurfuryl (meth) acrylate, 2-hydroxy-3-phenoxypropyl (meth) acrylate, diethylene glycol (meth) acrylate, polyethylene glycol (meth) Acrylate, 2- (dimethylamino) ethyl (meth) acrylate, N, N-dimethylacrylamide, N-methylol a (meth) acrylic acid, N-vinylpyrrolidone, styrene, o-, m-, P
-Methoxystyrene, o-, m-, Pt-butoxystyrene, o-, m-, P-chloromethylstyrene and the like. These may be random-copolymerized or block-copolymerized with two or more kinds of monomers. Further, a monomer may be gradually added during the polymerization to perform copolymerization.

Living radical polymerization is usually -50 to 2
It is carried out at a temperature of 00 ° C, preferably 0-150 ° C. Then, the reversible change of the redox conjugate complex in the redox catalyst is initiated by adding the polymerization initiator and the radical polymerizable monomer to the metal complex (high valence complex). At this time, the amount of the high valent metal used is not particularly limited, but is usually 10 ⁻⁴ to as a concentration in the reaction system.
It is 10 ^-1 mol / l, preferably 10 ^-3 to 10 ^-1 mol / l. And, usually 0.01 to 100 with respect to the initiator.
(Molar ratio), preferably 0.1 to 50 (molar ratio).

In the present invention, the low valent metal (M) ⁿ does not have to coexist at the start of the polymerization, and the low valent metal (M) ⁿ and the high valent metal (M) ^{n +} at the start of the polymerization are not necessary. ¹ and the molar ratio of ^{(M) n / (M)} n + 1 is 70 / 30-0 / 10
0, preferably 50/50 to 0/100, and more preferably 20/80 to 0/100. That is, the low valence metal (M) ⁿ is preferably not present at the start of polymerization when it is unstable depending on the type of metal and organic ligand or when the polymerization initiation efficiency is low depending on the type of initiator to be combined.

In the present invention, after the polymerization, the residual monomer and / or solvent is distilled off, reprecipitation is carried out in a suitable solvent, the precipitated polymer is filtered or centrifuged, and the polymer is washed and dried according to a well-known method. You can do it. The transition metal compound can be removed from the polymerization solution by passing through a column or pad of alumina, silica or clay. In addition, a method of dispersing a metal adsorbent in a polymerization solution and treating it can also be adopted. If desired, the metal component may remain in the polymer. The obtained polymer is subjected to size exclusion chromatography, NM according to well-known techniques.
It can be analyzed by R spectrum or the like.

As the solvent used for reprecipitation, water; C5 such as pentane, hexane, heptane, cyclohexane, etc.
C8 alkanes; C5-C8 cycloalkanes; C1-C6 alcohols such as methanol, ethanol, isopropanol and the like. Of these, water, hexane, methanol or mixtures thereof are preferred.

The number average molecular weight of the polymer obtained in the present invention is usually 250 to 500000, preferably 500 to 2
It is 50,000 and the molecular weight distribution (weight average molecular weight / number average molecular weight) is usually 1.8 or less, preferably 1.5 or less.

In the present invention, since it is living polymerization, the polymerization can be freely started and ended. In addition, the polymer has a functional group "X" necessary to initiate further polymerization, so that after the first monomer is consumed in the polymerization, the second monomer is on the growing polymer chain. Can be added to form a second block of By adding the same or different monomers,
Multi-block copolymers can be prepared.

The polymer obtained in the present invention is directly
Elastomer, engineering resin, paint, adhesive,
In addition to being used as inks and image forming compositions, it is also used as an additive for cement modifiers, dispersants, emulsifiers, surfactants, viscosity coefficient improvers, paper additives, antistatic agents, coating agents, resin modifiers, etc. used. Further, the polymer obtained in the present invention is used as an intermediate for larger polymer products such as polyurethane, as a water treatment chemical, a composite part, a cosmetic, a hair product, an intestinal dilator, a diagnostic agent, a sustained release composition, etc. It can be used as a pharmaceutical agent.

[0039]

EXAMPLES The present invention will be described in more detail with reference to examples below, but the present invention is not limited to the following examples as long as the gist thereof is not exceeded. In the following examples, molecular weight measurements were made using gel permeation chromatography calibrated with polystyrene standards.

Example 1 Methyl-2-bromoisobutyrate (23.9 mg, 0.132 mmol) and copper (II) were added to 10 mL-vial.
Trifluoromethanesulfonate (95.1 mg, 0.
263 mmol), 6 '-{(1R, 2R, 4R) -2
-Exo-hydroxy-1,7,7-trimethylbicyclo [2.2.1] heptan-2-endo-yl} 2,2'-
Bipyridine (24.2 mg, 0.0526 mmol),
Anisole (2.6 mL) was added and stirred for about 10 minutes. 1-phenylethylmethacrylate (5
(00 mg, 2.68 mmol) was added and stirred. This reaction solution was placed in 10 mL of a stirring bar-containing 10 mL test tubes with a screw and capped with 0.3 mL each,
The reaction was carried out by heating to 90 ° C.

After completion of the reaction, methanol was added to terminate the polymerization, and the monomer conversion rate was determined by gas chromatography to be 40%. The remaining polymerization solution was passed through a short activated alumina calum to remove the metal salt, the solvent was distilled off under reduced pressure, and the polymer was purified by reprecipitating twice with chloroform-methanol and dried under reduced pressure. The obtained polymer had a molecular weight of 12,200 and a molecular weight distribution of 1.42.

Example 2 542 mg of bis (trifluoromethanesulfonate) copper (II) was placed in a reaction flask equipped with a condenser substituted with nitrogen, a nitrogen introduction tube, a stirrer and a thermometer, and separately.
In the flask, 30 g of anisole, 38.4 g of n-butyl acrylate, and triethanolamine (ligand) 2
A mixed solution of 24 mg and 272 mg of methyl bromoisobutyrate (polymerization initiator) was bubbled with nitrogen for 15 minutes, then charged into the above reaction flask and polymerized at 105 ° C. for 3 hours. After completion of the polymerization, tetrahydrofuran (T
HF) was diluted with 100 ml and passed through a column packed with 30 g of activated alumina to remove the copper component. Then
The mixture was added dropwise to a mixed solvent of water / methanol = 1/5 for reprecipitation and dried to obtain 20.1 g of a colorless transparent polymer.
The number average molecular weight of the obtained polymer was 17,200, and the molecular weight distribution was 1.21.

Example 3 A reaction flask equipped with a condenser substituted with nitrogen, a nitrogen introduction tube, a stirrer and a thermometer was charged with 542 mg (1.5 mmol) of copper (II) bis (trifluoromethanesulfonate), and charged separately. , Anisole 30 in the flask
g, 2-ethylhexyl acrylate 55.3 g (0.
3 mol), triethanolamine 224 mg (1.5
1) of a mixed solution of 260 mg (0.75 mmol) of dimethyl 2,6-dibromo-1,7-heptanedioate.
After bubbling nitrogen for 5 minutes, the mixture was charged into the above reaction flask and polymerized at 100 ° C. for 6 hours. After completion of polymerization
It was diluted with 100 ml of THF and passed through a column packed with 50 g of activated alumina to remove the copper component. Then
The solution was added dropwise to methanol for reprecipitation and dried to obtain 25.2 g of a colorless transparent polymer. The number average molecular weight of the obtained polymer was 24500 and the molecular weight distribution was 1.42.

[0044]

According to the present invention described above, there is provided a method for producing a polymer comprising a radical-polymerizable monomer, wherein an atom transfer using an initiator system in which a catalyst can be easily handled and an initiator has a wide selection range. The manufacturing method by the radical radical polymerization method is provided, and the industrial value of the present invention is great.

Claims (3)

[Claims] 1. An organic halide or a sulfonyl halide compound is used as a polymerization initiator, and at least one radical-polymerizable compound is used in the presence of a redox catalyst composed of a metal complex represented by the following general formula (1). A method for producing a polymer comprising a radical-polymerizable monomer, which comprises polymerizing the monomer. Embedded image (M) ^{n + 1} Z _m (1) (where M is at least one transition metal selected from Groups 7 to 11 of the periodic table, n is an integer of 1 or more, m is an integer of 1 to 4, (M) ^{n + 1} is a high valence state that can be reduced, and Z is
It represents an organic ligand coordinated with an oxygen atom, a nitrogen atom, a phosphorus atom, a sulfur atom or a carbon atom. ) 2. The high valence metal (M) ^{n + 1} is Cu ²⁺ , N
i ⁺ , Ni ²⁺ , Ni ³⁺ , Pd ⁺ , Pd ²⁺ , Pt ⁺ , P
t ²⁺ , Pt ³⁺ , Rh ²⁺ , Rh ³⁺ , Rh ⁴⁺ , Co ²⁺ , Co
³⁺ , Ir ⁺ , Ir2 ⁺ , Ir3 ⁺ , Ir4 ⁺ , Fe3 ⁺ , R
u ³⁺ , Ru ⁴⁺ , Ru ⁵⁺ , Ru ⁵⁺ , Os ³⁺ , Os ⁴⁺ , Re
^The method according to claim 1, wherein the method is at least one selected from the group ^{consisting of 3+} , Re ⁴⁺ , Re ⁵⁺ , Re ⁷⁺ , Mn ³⁺ and Mn ⁴⁺ . 3. The high valence metal (M) ^{n + 1} is Cu ²⁺ , N
^{i 3+, Fe 3+, Ru 3} +, The method according to claim 1 or 2, which is one selected from the group of Ru ^4+.